Carboxylic acid amide benzothiophenecarboxamide s-oxides

ABSTRACT

New benzothiophenecarboxamide S-oxides of the formula (I) ##STR1## in which R 1  represents optionally substituted alkyl, or represents alkenyl or alkinyl, or represents in each case optionally substituted cycloalkyl or cycloalkylalkyl, or represents in each case optionally substituted aralkyl, aralkenyl, aralkinyl or aryl and 
     R 2  represents hydrogen or optionally substituted alkyl, or 
     R 1  and R 2  together with the nitrogen atom to which they are bonded represent an optionally substituted heterocycle, 
     R 3 , R 4 , R 5  and R 6  independently of one another in each case represent hydrogen, halogen, cyano, nitro, alkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy or halogenoalkylthio, and 
     R 1  represents hydrogen or halogen, 
     a process for their preparation, and their use as microbicides in plant protection and in the protection of materials. 
     New intermediates for the preparation of substances of the formula (I).

The invention relates to new benzothiophenecarboxamide S-oxides, to aprocess for their preparation, and to their use as microbicides in plantprotection and in the protection of materials.

It has been disclosed that certain benzothiophenecarboxamideS,S-dioxides, such as, for example, the compoundN-(methyl)-benzothiophene-2-carboxamide S,S-dioxide, have fungicidalproperties (cf., for example, DE-OS (German Published Specification)4,115,184).

However, the effectiveness of these prior-art compounds is not entirelysatisfactory in all fields of application, in particular when lowamounts and concentrations are applied.

New benzothiophenecarboxamide S-oxides of the formula (I) ##STR2## havebeen found in which R¹ represents optionally substituted alkyl, orrepresents alkenyl or alkinyl, or represents in each case optionallysubstituted cycloalkyl or cycloalkylalkyl, or represents in each caseoptionally substituted aralkyl, aralkenyl, aralkinyl or aryl and

R² represents hydrogen or optionally substituted alkyl, or

R¹ and R.sup. 2 together with the nitrogen atom to which they are bondedrepresent an optionally substituted heterocycle,

R³, R⁴, R^(s) and R⁶ independently of one another in each case representhydrogen, halogen, cyano, nitro, alkyl, alkoxy, alkylthio,halogenoalkyl, halogenoalkoxy or halogenoalkylthio, and

R⁷ represents hydrogen or halogen.

If appropriate, the compounds of the formula (I) can exist in the formof geometric and/or optical isomers or variously composed mixtures ofisomers, depending on the nature of the substituents. The pure isomersand also the isomer mixtures are claimed according to the invention.

Furthermore, it has been found that the new substitutedthiophenecarboxamides of the formula (I) ##STR3## in which R¹ representsoptionally substituted alkyl, or represents alkenyl or alkinyl, orrepresents in each case optionally substituted cycloalkyl orcycloalkylalkyl, or represents in each case optionally substitutedaralkyl, aralkenyl, aralkinyl or aryl and

R² represents hydrogen or optionally substituted alkyl, or

R¹ and R² together with the nitrogen atom to which they are bondedrepresent an optionally substituted heterocycle,

R³, R⁴, R⁵ and R⁶ independently of one another in each case representhydrogen, halogen, cyano, nitro, alkyl, alkoxy, alkylthio,halogenoalkyl, halogenoalkoxy or halogenoalkylthio, and

R⁷ represents hydrogen or halogen,

are obtained when benzothiophenecarboxamides of the formula (II)##STR4## in which R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have the abovementionedmeaning

are reacted with an oxidant, if appropriate in the presence of a diluentand if appropriate in the presence of a catalyst.

Finally, it has been found that the novel benzothiophenecarboxamideS-oxides of the formula (I) have powerful microbicidal properties andcan be employed both in plant protection and in the protection ofmaterials.

Surprisingly, the benzothiophenecarboxamide S-oxides of the formula (I)according to the invention display a considerably better effectivenessagainst plant-pathogenic microorganisms than, for example, the compoundN-(methyl)-benzothiophene-2-carboxamide S,S-dioxide, which is aprior-art active compound having the same direction of action andsimilar constitution.

Formula (I) provides a general definition of thebenzothiophenecarboxamide S-oxides according to the invention.

R¹ preferably represents straight-chain or branched alkyl having 1 to 20carbon atoms which is optionally substituted by a nitrogen-bonded,saturated heterocycle which has 1 nitrogen atom and 2 to 6 carbon atomsand which can additionally be substituted by halogen, in each casestraight-chain or branched alkyl or alkoxy, each of which has 1 to 4carbon atoms, or straight-chain or branched halogenoalkyl having 1 to 4carbon atoms and 1 to 9 identical or different halogen atoms, orrepresents in each case straight-chain or branched halogenoalkyl,cyanoalkyl, hydroxyalkyl, alkoxyalkyl or alkoxycarbonylalkyl, each ofwhich has 1 to 8 carbon atoms in the individual alkyl moieties, orrepresents straight-chain or branched alkenyl having 2 to 12 carbonatoms, or represents straight-chain or branched alkinyl having 2 to 12carbon atoms, or represents cycloalkylalkyl or cycloakyl, each of whichhas 3 to 7 carbon atoms in the cycloalkyl moiety and, if appropriate, 1to 6 carbon atoms in the straight-chain or branched alkyl moiety andeach of which is optionally mono- to hexa-substituted in the cycloalkylmoiety by identical or different substituents, suitable cycloalkylsubstituents in each case being:

halogen, in each case straight-chain or branched alkyl having 1 to 4carbon atoms or in each case straight-chain or branched halogenoalkylhaving 1 to 4 carbon atoms and 1 to 9 identical or different halogenatoms; furthermore represents arylalkyl, arylalkenyl, arylalkinyl oraryl, each of which has 6 or 10 carbon atoms in the aryl moiety and, ifappropriate, up to 12 carbon atoms in the in each case straight-chain orbranched alkyl, alkenyl or alkinyl moiety and each of which isoptionally mono- to pentasubstituted in the aryl moiety by identical ordifferent substituents, suitable aryl substituents in each case being:

halogen, hydroxyl, cyano, nitro, formylamido, in each casestraight-chain or branched alkyl, alkoxy or alkylthio, each of which has1 to 4 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, in each casestraight-chain or branched halogenoalkyl, halogenoalkoxy orhalogenoalkylthio, each of which has 1 to 4 carbon atoms and 1 to 9identical or different halogen atoms, in each case straight-chain orbranched alkylcarbonyl, alkoxycarbonyl, aminocarbonyl,N-alkylaminocarbonyl, N,N-dialkylaminocarbonyl, alkylcarbonylamino,N-alkyl-alkylcarbonylamino, N-alkyl-formylcarbonylamino oralkoximinoalkyl, each of which has 1 to 4 carbon atoms in the individualalkyl moieties, and phenyl which is optionally mono-substituted orpolysubstituted by identical or different substituents from the seriesconsisting of halogen and straight-chain or branched alkyl having 1 to 4carbon atoms.

R² preferably represents hydrogen, or represents straight-chain orbranched alkyl having 1 to 6 carbon atoms which is optionallymonosubstituted or polysubstituted by identical or differentsubstituents, suitable substituents in each case being:

hydroxyl, halogen, cyano, and in each case straight-chain or branchedalkoxy, alkoxycarbonyl or dialkylamino, each of which has 1 to 6 carbonatoms in the individual alkyl moieties, or

R¹ and R² preferably together with the nitrogen atom to which they arebonded represent a saturated five- to seven-membered heterocycle whichcan optionally contain one or two further hetero atoms--in particularnitrogen, oxygen and/or sulphur--and which is optionally monosubstitutedor polysubstituted by identical or different substituents, suitablesubstituents in each case being:

halogen, in each case straight-chain or branched alkyl or alkoxy, eachof which has 1 to 4 carbon atoms, or straight-chain or branchedhalogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical ordifferent halogen atoms.

R³, R⁴, R⁵ and R⁶ preferably independently of one another in each caserepresent hydrogen, halogen, cyano, nitro, or represent in each casestraight-chain or branched alkyl, alkoxy, alkylthio, halogenoalkyl,halogenoalkoxy or halogenoalkylthio, each of which has 1 to 6 carbonatoms and, if appropriate, 1 to 13 identical or different halogen atoms.

R⁷ preferably represents hydrogen, fluorine, chlorine or bromine.

R¹ particularly preferably represents straight-chain or branched alkylhaving 1 to 18 carbon atoms which is optionally substituted by anitrogen-bonded, saturated heterocycle which has I nitrogen atom and 2to 6 carbon atoms and which can additionally be substituted by halogen,in each case straight-chain or branched alkyl or alkoxy, each of whichhas 1 to 4 carbon atoms, or straight-chain or branched halogenoalkylhaving 1 to 4 carbon atoms and 1 to 9 identical or different halogenatoms, or represents in each case straight-chain or branchedhalogenoalkyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl oralkoxycarbonylalkyl, each of which has 1 to 4 carbon atoms in theindividual alkyl moieties, or represents straight-chain or branchedalkenyl having 2 to 8 carbon atoms, or represents straight-chain orbranched alkinyl having 2 to 8 carbon atoms, or representscycloalkylalkyl or cycloalkyl, each of which has 3 to 6 carbon atoms inthe cycloalkyl moiety, and, if appropriate, 1 to 4 carbon atoms in thestraight-chain or branched alkyl moiety and each of which is optionallymono- to tetrasubstituted in the cycloalkyl moiety by identical ordifferent substituents, suitable cycloalkyl substituents in each casebeing:

fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s-or t-butyl, chloromethyl, dichloromethyl or trifluoromethyl; furthermorerepresents arylalkyl, arylalkenyl, arylalkinyl or aryl, each of whichhas 6 or 10 carbon atoms in the aryl moiety and, if appropriate, up to 8carbon atoms in the in each case straight-chain or branched alkyl,alkenyl or alkinyl moiety and each of which is optionally mono- topentasubstituted in the aryl moiety by identical or differentsubstituents, suitable aryl substituents in each case being:

halogen, hydroxyl, cyano, nitro, formylamido, in each casestraight-chain or branched alkyl, alkoxy or alkylthio, each of which has1 to 4 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, in each casestraight-chain or branched halogenoalkyl, halogenoalkoxy orhalogenoalkylthio, each of which has 1 to 4 carbon atoms and 1 to 9identical or different halogen atoms, in each case straight-chain orbranched alkylcarbonyl, alkoxycarbonyl, aminocarbonyl,N-alkylaminocarbonyl, N,N-dialkylaminocarbonyl, alkylcarbonylamino,N-alkyl-alkylcarbonylamino, N-alkyl-formylcarbonylamino oralkoximinoalkyl, each of which has 1 to 4 carbon atoms in the individualalkyl moieties, and phenyl which is optionally monosubstituted totrisubstituted by identical or different substituents from the seriesconsisting of halogen and straight-chain or branched alkyl having 1 to 4carbon atoms.

R² particularly preferably represents hydrogen or representsstraight-chain or branched alkyl having 1 to 4 carbon atoms which isoptionally monosubstituted or polysubstituted by identical or differentsubstituents, suitable substituents being:

hydroxyl, halogen, cyano, and in each case straight-chain or branchedalkoxy, alkoxycarbonyl or dialkylamino, each of which has 1 to 4 carbonatoms in the individual alkyl moieties, or

R¹ and R² particularly preferably together with the nitrogen atom towhich they are bonded represent a heterocycle of the formula ##STR5##which is optionally monosubstituted to tetrasubstituted by identical ordifferent substituents, suitable substituents in each case being:fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, methoxy,ethoxy, chloromethyl, trichloromethyl, dichloromethyl, trifluoromethylor difluoromethyl.

R³, R⁴, R⁵ and R⁶ particularly preferably independently of one anotherin each case represent hydrogen, halogen, cyano, nitro, or represent ineach case straight-chain or branched alkyl, alkoxy, alkylthio,halogenoalkyl, halogenoalkoxy or halogenoalkylthio, each of which has 1to 4 carbon atoms and, if appropriate, 1 to 9 identical or differenthalogen atoms.

R⁷ particularly preferably represents hydrogen, chlorine or bromine.

R¹ very particularly preferably represents methyl, ethyl, n- ori-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, n- ori-heptyl, n- or i-octyl, n- or i-nonyl, n- or i-decyl, n- or i-dodecyl,n- or i-octadecyl, or represents allyl, n- or i-butenyl, n- ori-pentenyl, n- or i-hexenyl, propargyl, n- or i-butinyl, n- ori-pentinyl, n- or i-hexinyl, chloromethyl, bromomethyl, chloroethyl,bromoethyl, chloropropyl, bromopropyl, cyanomethyl, cyanoethyl,cyanopropyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, methoxymethyl,methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl,methoxycarbonylmethyl, methoxycarbonylethyl, methoxycarbonylpropyl,ethoxycarbonylmethyl, ethoxycarbonylethyl, ethoxycarbonylpropyl,propoxycarbonylmethyl, propoxycarbonylethyl, propoxycarbonylpropyl;furthermore represents cyclopropyl, cycloropylmethyl, cyclopropylethyl,cyclopropylpropyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl,cyclopentylpropyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl orcyclohexylpropyl, each of which is optionally mono- to tetrasubstitutedin the cycloalkyl moiety by identical or different substituents from theseries consisting of fluorine, chlorine, bromine, methyl, ethyl, n- ori-propyl, chloromethyl, dichloromethyl or trifluoromethyl; furthermorerepresents phenylalkyl, phenylalkenyl, phenylalkinyl, phenyl ornaphthyl, each of which has, if appropriate, up to 6 carbon atoms in thestraight-chain or branched alkyl, alkenyl or alkinyl moiety and each ofwhich is optionally mono- to trisubstituted in the aryl moiety byidentical or different substituents, suitable aryl substituents in eachcase being:

fluorine, chlorine, bromine, hydroxyl, cyano, nitro, methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy,n-, i-, s- or t-butoxy, methylthio, ethylthio, cyclopropyl, cyclopentyl,cyclohexyl, cycloheptyl, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, methylcarbonyl, ethylcarbonyl, methoxycarbonyl,ethoxycarbonyl, aminocarbonyl, N-methylamino-carbonyl,N,N-dimethylaminocarbonyl, N-ethylaminocarbonylN,N-diethylaminocarbonyl, N-formylamino, N-acetylamino,N-methyl-N-formylamino, N-methyl-N-acetylamino, N-ethyl-N-formylamino,N-ethyl-N-acetylamino, methoximinomethyl, methoximinoethyl,ethoximinomethyl, ethoximinoethyl or phenyl which is optionally mono- totrisubstituted by identical or different substituents from the seriesconsisting of fluorine, chlorine, bromine, methyl and ethyl.

R² very particularly preferably represents hydrogen, methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl,hydroxymethyl, hydroxyethyl, hydroxypropyl, chloromethyl, bromomethyl,chloroethyl, bromoethyl, chloropropyl, bromopropyl, cyanomethyl,cyanoethyl, cyanopropyl, methoxymethyl, methoxyethyl, methoxypropyl,ethoxymethyl, ethoxyethyl, ethoxypropyl, methoxycarbonylmethyl,methoxycarbonylethyl, methoxycarbonylpropyl, ethoxycarbonylmethyl,ethoxycarbonylethyl, ethoxycarbonylpropyl, propoxycarbonylmethyl,propoxycarbonylethyl, propoxycarbonylpropyl, dimethylaminomethyl,diethylaminomethyl, dipropylaminomethyl, dimethylaminoethyl,diethylaminoethyl, dipropylaminoethyl, dimethylaminopropyl,diethylaminopropyl or dipropylaminopropyl or

R¹ and R² very particularly preferably together with the nitrogen atomto which they are bonded represent a heterocycle of the formula ##STR6##which is optionally monosubstituted to trisubstituted by identical ordifferent substituents from the series consisting of methyl and ethyl.

R³, R⁴, R⁵ and R⁶ very particularly preferably independently of oneanother in each case represent hydrogen, fluorine, chlorine, bromine,cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio,ethylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio.

R⁷ very particularly preferably represents hydrogen or chlorine.

If, for example, N-(3-chlorophenyl)-benzothiophene-2-carboxamide is usedas starting compound and m-chloroperbenzoic acid as the oxidant, thecourse of the reaction of the process according to the invention can berepresented by the following equation: ##STR7##

Formula (II) provides a definition of the benzothiophenecarboxamidesrequired as starting substances for carrying out the process accordingto the invention. In this formula (II), R¹, R², R³, R⁴, R⁵, R⁶ and R⁷preferably represent those radicals which have already been mentioned inconnection with the description of the compounds of the formula (I)according to the invention as being preferred for these substituents.The benzothiophenecarboxamides of the formula (II) are known or can beobtained in analogy to known processes (cf., for example, DE 3 832 846;DE 3 832 848; EP 374 048; EP 253 650; Ind. J. Chem. Sect. B, 23B, 38-411984!; Tetrahedron 34, 3545-3551 1978!; Collect. Czech. Chem. Commun.51, 2002-2012 1986!; J. Org. Chem. 40, 3037-3045 1975!; Liebigs Ann.Chem. 760, 37-87 1972! and the preparation examples).

Benzothiophenecarboxamides of the formula (IIa) ##STR8## in which R¹,R², R³, R⁴, R⁵ and R⁶ have the abovementioned meaning

are alternatively also obtained by a new process which is also providedby the invention, by reacting benzothiophenecarboxamides of the formula(IIb) ##STR9## in which R¹, R², R³, R⁴, R⁵ and R⁶ have theabovementioned meaning with molecular hydrogen in the presence of adiluent and in the presence of a catalyst and, if appropriate, in thepresence of a base.

It must be considered as surprising and unforeseeable by the expert thatthis reductive dehalogenation reaction with catalytically activatedhydrogen does not simultaneously result in hydrogenation of the doublebond in the benzothiophene moiety of the molecule.

A particular advantage of this process for synthesizing thebenzothiophenecarboxamides of the formula (IIa) which are used asprecursors is the fact that, as opposed to the prior-an processes (of.,for example, DE 4 115 184), the starting material used in the presentcase, the starting materials are particularly readily accessible andinexpensive cinnamic acid derivatives whose reaction with thionylchloride yields the benzothiophenecarboxamides of the formula (IIb)required in a smooth reaction (cf., for example, DE 3 832 846; DE 3 832848).

Suitable diluents for carrying out this dehalogenation process accordingto the invention are all customary inorganic solvents. These include, inparticular, aliphatic, alicyclic or aromatic hydrocarbons such as, forexample, benzene, benzene, toluene, xylene, petroleum ether, hexane,cyclohexane; ethers, such as diethyl ether, diisopropyl ether, methyltert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran,ethylene glycol dimethyl ether or ethylene glycol diethyl ether;diethylene glycol dimethyl ether or diethylene glycol diethyl ether, oranisole; amides, such as formamide, N,N-dimethylformamide,N,N-dibutylformamide, N,N-dimethylacetamide, N-methylformanilide,N-methylpyrrolidone, N-methyl-ε-caprolactam or hexamethylphosphorictriamide; esters, such as methyl acetate, ethyl acetate or butylacetate; alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-,s- or t-butanol, ethylene glycol, ethylene glycol monomethyl ether orethylene glycol monoethyl ether, their mixtures with water, or purewater. Polar diluents are particularly preferably used.

Suitable catalysts for carrying out this dehalogenation processaccording to the invention are customary reduction catalysts. Catalystswhich are particularly preferably used are noble-metal catalysts, suchas, for example, palladium or palladium salts, or else Raney catalysts,such as Raney nickel or Raney cobalt, if appropriate on a suitablesupport material, such as, for example, carbon or silicon dioxide.

The dehalogenation process according to the invention is preferablycarried out in the presence of a base. Suitable bases are all customaryinorganic or organic bases. These include, for example, the hydroxides,acetates, carbonates or hydrogen carbonates of alkaline earth metals,alkali metals or of ammonium, such as, for example, sodium hydroxide,potassium hydroxide, ammonium hydroxide, sodium acetate, potassiumacetate, calcium acetate, ammonium acetate, sodium carbonate, potassiumcarbonate, potassium hydrogen carbonate, sodium hydrogen carbonate orammonium carbonate, and also tertiary amines, such as trimethylamine,triethylamine, tributylamine, N,N-dimethylaniline,N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, pyridine,N-methylpiperidine, N,N-dimethylaminopyridine, diazabicyclooctane(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU). Ifappropriate, it is also possible to use a suitable excess of basesimultaneously as the diluent.

When carrying out the dehalogenating process according to the invention,the reaction temperatures can be varied within a substantial range. Ingeneral, the process is carded out at temperatures between 10° C. and150° C., preferably at temperatures between 30° C. and 120° C.

The dehalogenation process according to the invention is customarilycarded out under pressure. In general, the process is carded out inpressure ranges between 1 bar and 150 bar, preferably between 2 bar and80 bar.

To carry out the dehalogenation process according to the invention,0.0001 to 1.0 mol, preferably 0.001 to 0.1 mol, of hydrogenationcatalyst and 1.0 to 5.0 mol, preferably 1.0 to 2.5 mol, of base aregenerally employed per mole of benzothiophenecarboxamide of the formula(IIb), and molecular hydrogen is then added at the temperature requireduntil the pressure required is established. The reaction is carried outand the reaction products are worked up and isolated in a generallycustomary manner (cf. in this context also the preparation examples).

Suitable oxidants for carrying out the oxidation reaction according tothe invention are all oxidants which can customarily be used for theoxidation of sulphur. Hydrogen peroxide or organic peracids, such as,for example, peracetic acid, 4-nitroperbenzoic acid or3-chloroperbenzoic acid, are preferably used.

Depending on the oxidant used, suitable diluents for carrying out theoxidation process according to the invention are inorganic or organicsolvents. The following are preferably used: alcohols, such as, forexample, methanol or ethanol, or their mixtures with water or purewater; acids, such as, for example, acetic acid, acetic anhydride orpropionic acid, or dipolar aprotic solvents, such as acetonitrile,acetone, ethyl acetate or dimethylformamide, and also optionallyhalogenated hydrocarbons, such as benzine, benzene, toluene, hexane,cyclohexane, petroleum ether, dichloromethane, dichloroethane,chloroform, carbon tetrachloride or chlorobenzene.

If appropriate, the oxidation process according to the invention canalso be carried out in the presence of a suitable catalyst. Suitablecatalysts which can be used are all those which can be used customarilyfor such sulphur oxidation reactions. Heavy metal catalysts arepreferably used; an example which may be mentioned in this context isammonium molybdate.

When carrying out the oxidation process according to the invention, thereaction temperatures can be varied within a substantial range. Ingeneral, the process is carried out at temperatures between -30° C. and+50° C., preferably at temperatures between 0° C. and +25° C.

To carry out the oxidation process according to the invention, 2.0 to10.0 mol, preferably 1.0 to 2.5 mol, of oxidant and, if appropriate,0.001 to 1.0 mol, preferably 0.005 to 0.05 mol, of catalyst aregenerally employed per mole of benzothiophene- carboxamide of theformula (II).

The reaction is carried out and the reaction products are worked up andisolated by customary, known processes (cf. in this context thepreparation examples).

The end products of the formula (I) are purified with the aid ofcustomary processes, for example by column chromatography or byrecrystallization. They are characterized with the aid of the meltingpoint or, in the case of compounds which do not crystallize, with theaid of the refractive index or proton nuclear resonance spectroscopy (¹H NMR).

The active compounds according to the invention have a powerfulmicrobicidal activity and can be employed as fungicides in plantprotection and in the protection of materials.

Fungicidal agents in plant protection are employed for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Some causative organisms of fungal diseases which come under the genericnames listed above may be mentioned as examples, but not by way oflimitation:

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonosporahumuli or Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Peronospora species, such as, for example, Peronospora pisi orPeronospora brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres orPyrenophora graminea (conidia form: Drechslera, synonym:Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus(conidia form: Drechslera, synonym: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilagoavenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae and

Pseudocercosporella species, such as, for example, Pseudocercosporellaherpotrichoides.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

The active compounds according to the invention can be employedparticularly successfully for combating diseases in fruit and vegetablegrowing, such as, for example, against the causative organism of tomatoblight (Phytophthora infestans) or for combating cereal diseases, suchas, for example, against the causative organism of net blotch of barley(Pyrenophora teres) or against the causative organism of leaf spot ofbarley or wheat (Cochliobolus sativus) or against the causative organismof glume blotch of wheat (Septoria nodorum) or for combating ricediseases, such as, for example, against the causative organism of riceblast disease (Pyricularia oryzae) or against the causative organism ofrice stem blight (Pellicularia sasakii). In addition, the activecompounds according to the invention also have a good in-vitro activity.

Moreover, the active compounds according to the invention can beemployed for protecting industrial materials against infection with, anddestruction by, undesired microorganisms.

Industrial materials in the present context are to be understood asmeaning non-living materials which have been prepared for use inindustry. For example, industrial materials which are intended to beprotected by active compounds according to the invention from microbialchange or destruction can be glues, sizes, papers and board, textiles,leather, wood, paints and plastic articles, cooling lubricants and othermaterials which can be infected with, or destroyed by, microorganisms.Parts of production plants, for example cooling-water circuits, whichmay be impaired by the multiplication of microorganisms may also bementioned within the scope of the materials to be protected. Industrialmaterials which may be mentioned within the scope of the presentinvention are preferably glues, sizes, papers and boards, leather, wood,paints, cooling lubricants and heat-transfer liquids, particularlypreferably wood.

The compounds according to the invention are preferably suitable for theprotection of paints against infection with, and destruction by,microorganisms.

Microorganisms which are capable of bringing about degradation of, orchange in, the industrial materials are, for example, bacteria, fungi,yeasts, algae and slime organisms. The active compounds according to theinvention preferably act against fungi, in particular moulds,wood-discolouring and wood-destroying fungi (Basidiomycetes) and againstslime organisms and algae.

Microorganisms of the following genera may be mentioned as examples:

Alternaria, such as Alternaria tenuis;

Aspergillus, such as Aspergillus niger;

Chaetomium, such as Chaetominum globosum;

Coniophora, such as Coniophora puteana;

Lentinus, such as Lentinus tigrinus;

Penicillium, such as Penicillium glaucum;

Polyporus, such as Polyporus versilicolor;

Aureobasidium, such as Aureobasidium pullulans;

Sclerophoma, such as Sclerophoma pityophila;

Trichoderma, such as Trichoderma viride;

Escherichia, such as Escherichia coil;

Pseudomonas, such as Pseudomonas aeruginosa;

Staphylococcus, such as Staphylococcus aureus.

Depending on their particular physical and/or chemical properties and onthe field of application, the active compounds can be converted to thecustomary formulations, such as solutions, emulsions, suspensions,powders, foams, pastes, granules, aerosols, very fine capsules inpolymeric substances and in coating compositions for seed, as well asULV cold mist and warm mist formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents, such as for example, alcohols can also beused as auxiliary solvents. As liquid solvents, there are suitable inthe main: aromatics, such as xylene, toluene or alkylnaphthalenes,chlorinated aromatics or chlorinated aliphatic hydrocarbons, such aschlorobenzenes, chloroethylenes, such as 1,2-dichloroethane or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample benzine or other mineral oil fractions, alcohols, such asethanol, isopropanol, butanol, benzyl alcohol or glycol as well as theirethers and esters, ketones, such as acetone, methyl ethyl ketone, methylisobutyl ketone or cyclohexanone, strongly polar solvents, such asdimethylformamide and dimethyl sulphoxide, as well as water; byliquefied gaseous extenders or carriers are meant liquids which aregaseous at ambient temperature and under atmospheric pressure, forexample aerosol propellants, such as halogenated hydrocarbons as well asbutane, propane, nitrogen and carbon dioxide; as solid carriers thereare suitable: for example ground natural minerals, such as kaolins,clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceousearth, and ground synthetic minerals, such as highly-disperse silica,alumina and silicates; as solid carriers for granules there aresuitable: for example crushed and fractionated natural rocks such ascalcite, marble, pumice, sepiolite and dolomite, as well as syntheticgranules of inorganic and organic meals, and granules of organicmaterial such as sawdust, coconut shells, maize cobs and tobacco stalks;as emulsifying and/or foam-forming agents there are suitable: forexample non-ionic and anionic emulsifiers, such as polyoxyethylene fattyacid esters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates aswell as albumen hydrolysis products; as dispersing agents there aresuitable: for example ligninsulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

When used in plant protection, the formulations in general comprisebetween 0.1 and 95 per cent by weight of active compound, preferablybetween 0.5 and 90%.

When used in plant protection, the active compounds according to theinvention can exist, in the formulations, in the form of a mixture withother known active compounds, such as fungicides, insecticides,acaricides and herbicides, and in the form mixtures with fertilizers andgrowth regulators.

The active compounds can be used as such, in the form of theirformulations or in the use forms prepared therefrom, such asready-to-use solutions, suspensions, wettable powders, pastes, solublepowders, dusts and granules. They are used in the customary manner, forexample by watering, spraying, atomizing, scattering, dusting, foaming,brushing on and the like. It is furthermore possible to apply the activecompounds by the ultra-low-volume method, or to inject the activecompound preparation, or the active compound itself, into the soil. Theseed of the plants can also be treated.

In the treatment of parts of plants, the active compound concentrationsin the use forms can be varied within a substantial range they aregenerally between 1 and 0.0001% by weight, preferably between 0.5 and0.001 % by weight.

In the treatment of seed, mounts of active compound of 0.001 to 50 g,preferably 0.01 to 10 g, are generally required per kilogram of seed.

In the treatment of the soil, active compound concentrations of 0.00001to 0.1% by weight, preferably 0.0001 to 0.02 % by weight, are requiredat the site of action.

The compositions used for the protection of industrial materialsgenerally comprise 10 1 to 95 %, preferably 10 to 75 %, of the activecompounds.

The use concentrations of active compounds according to the inventiondepend on the species and the occurrence of the microorganisms to becombated and on the composition of the material to be protected. Theoptimum dosage rate can be determined by test series. In general, theuse concentrations are in the range from 0.001 to 5 % by weight,preferably from 0.05 to 1.0 by weight, relative to the material to beprotected.

The effectiveness and the spectrum of action of the active compoundswhich can be used according to the invention, or of the compositions,concentrates or quite generally formulations which can be preparedtherefrom, can be increased by adding, if appropriate, otherantimicrobially active compounds, fungicides, bactericides, herbicides,insecticides or other active compounds for broadening the spectrum ofaction or for achieving specific effects, such as, for example, theadditional protection against insects. These mixtures may have a broaderspectrum of action than the compounds according to the invention.

In many cases, synergistic effects are obtained, i.e. the effectivenessof the mixture exceeds the effectiveness of the individual components.Particularly components of mixtures are, for example, the followingcompounds:

Sulphenamides, such as dichlorfluanid (Euparen), tolyfluanid(Methyleuparen), folpet, fluorfolpet;

Benzimidazoles, such as carbendazim (MBC), benomyl, fuberidazole,thiabendazole or their salts;

Thiocyanates, such as thiocyanatomethylthiobenzothiazole (TCMTB),methylenebisthiocyanate (MBT);

Quaternary ammonium compounds, such as benzyldimethyltetradecylammoniumchloride, benzyl-dimethyl-dodecyl-ammonium chloride,dodecyl-dimethyl-ammonium chloride;

Morpholine derivatives, such as C₁₁ -C₁₄-4-alkyl-2,6-dimethyl-morpholine homologs (tridemorph), (±)-cis-4-tert-butylphenyl)-2-methylpropyl!-2,6-dimethylmorpholine(fenpropimorph), falimorp;

Phenols, such as o-phenylphenol, tribromophenol, tetrachlorophenol,pentachlorophenol, 3-methyl-4-chlorophenol, dichlorophene, chlorophene,or their salts;

Azoles, such as triadimefon, triadimenol, bitertanol, tebuconazole,propiconazole, azaconazole, hexaconazole, prochloraz, cyproconazole,1-(2-chlorocyclopropyl)-2-(1-chlorocyclopropyl)-3-(1,2,4-triazol-1-yl)-propan-2-olor1-(2-chlorophenyl)-2-(1,2,4-triazol-1-yl-methyl)-3,3-dimethyl-butan-2-ol;

Iodopropargyl derivatives, such as iodopropargyl butylcarbamate (IPBC),iodopropargylchlorophenyl formal, iodopropargyl phenylcarbamate,iodopropargyl hexylcarbamate, iodopropargyl cyclohexylcarbamate andiodopropargyl oxyethylphenylcarbamate;

Iodine derivatives such as diodomethyl-p-aryl sulphones, for examplediiodomethyl-p-tolyl sulphone;

Bromine derivatives such as bromopol;

Isothiazolines such as N-methylisothiazolin-3-one,5-chloro-N-methyliaothiazolin-3-one,4,5-dichloro-N-octylisothiazolin-3-one, N-octylisothiazolin-3-on(octilinone);

Benzisothiazolinones, cyclopentene-isothiazolines;

Pyridines such as 1-hydroxy-2-pyridinethione (and their Na, Fe, Mn andZn salts), tetrachloro-4-methylsulphonylpyridine;

Metal soaps, such as tin napthenate, tin octoate, tin 2-ethylhexanoate,tin oleate, tin phosphate, tin benzoate, copper napthenate, copperoctoate, copper 2-ethylhexanoate, copper oleate, copper phosphate,copper benzoate, zinc napthenate, zinc octoate, zinc 2-ethylhexanoate,zinc oleate, zinc phosphate and zinc benzoate, and oxides such as TBTO,Cu₂ O, CuO, ZnO;

Organotin compounds, such as tributyltin naphtenate and tributyltinoxide;

Dialkyldithiocarbamates, such as Na and Zn salts ofdialkyldithiocarbamates, tetramethyltiuramidisulfide (TMTD);

Nitriles, such as 2,4,5,6-tetrachloroisophthalonitrile (chlorthalonil)and other microbicides having an activated halogen group, such asCl--Ac, MCA, tectamer, bromopol, bromidox;

Benzothiazoles, such as 2-mercaptobenzothiazoles; s.a. dazomet;

Quinolines, such as 8-hydroxyquinoline;

Formaldehyde-releasing compounds, such as benzyl alcoholmono(poly)-hemiformal, oxazolidines, hexahydro-2-triazines,N-methylolchloroacetamide;

Tris-N-(cyclohexyldiazeniumdioxy)-aluminium,N-(cyclohexyldiazeniumdioxy)-tri-butyltin or K salts,bis-(N-oyclohexyl)diazinium -(dioxy-copper or aluminium).

Preferred insecticides which are added are:

Phosphoric esters, such as azinphos-ethyl, azinphos-methyl,1-(4-chlorophenyl)-4-(O-ethyl, S-propyl)phosphoryloxypyrazole (TIA-230),chlorpyrifos, coumaphos, demeton, demeton-S-methyl, diazinon,dichlorfos, dimethoate, ethoprophos, etrimfos, fenitrothion, fention,heptenophos, parathion, parathion-methyl, phosalone, phoxim,pirimiphos-ethyl, pirimiphos-methyl, profenofos, prothiofos, sulprofos,triazophos and trichlorphon.

Carbamates such as aldicarb, bendiocarb, BPMC (2-(1-methylpropyl)phenylmethylcarbamate), butocarboxim, butoxycarboxim, carbaryl, carbofuran,carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb,promecarb, propoxur and thiodicarb;

Pyrethroids, such as allethrin, alphamethrin, bioresmethrin, byfenthrin(FMC 54800), cycloprothrin, cyfluthrin, decamethrion, cyhalothrin,cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl)-cyclopropanecarboxylate,fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin,fluvalinate, permethrin and resmethrin, nitroimino and nitromethylenecompounds such as 1-(6-chloro-3-pyridinyl)-methyl-!-4,5-dihydro-N-nitro-1H-imidazol-2-amine(imidachloprid).

Organosilicon compounds, preferably dimethyl(phenyl)silylmethyl3-phenoxybenzyl ethers, such as, for example,dimethyl-(4-ethoxyphenyl)-silylmethyl 3-phenoxybenzyl ether ordimethyl(phenyl)-silylmethyl 2-phenoxy-6-pyridylmethyl ethers, such as,for example, dimethyl(9-ethoxyphenyl)-silylmethyl2-phenoxy6-pyridylmethyl ethers, or (phenyl)3-(3-phenoxyphenyl)propyl!(dimethyl)-silanes, such as, for example,(4-ethoxyphenyl)- 3(4-fluoro-3-phenoxyphenyl)-propyl!dimethylsilanes.

Other active compounds which are suitable are algicides, molluscicidesand active compounds against sea animals which populate, for example,ships' bottom paints.

The preparation of active compounds and their use according to theinvention are illustrated by the examples which follow.

PREPARATION EXAMPLES Example 1 ##STR10##

9.1 g (0.039 mol) of m-chloroperbenzoic acid (73 per cent strength) areadded to 11.1 g (0.039 mol) ofN-(3-chlorophenyl)-benzothiophene-2-carboxamide in 500 ml ofdichloromethane at room temperature, with stirring, and the mixture issubsequently stirred at room temperature for 12 hours. For working-up,precipitated product is filtered off with suction, washed withdichloromethane and dried in vacuo at 50° C.

8.4 g (71% of theory) ofN-(3-chlorophenyl)-benzothiophene-2-carboxamide-S-oxide of melting point257°-258° C. are obtained.

Preparation of the starting compounds

Example II-1 ##STR11##

A solution of 3.2 g (0.025 mol) of 3-chloroaniline and 2.53 g oftriethylamine in 30 ml of toluene is added to 5.0 g (0.025 mol) ofbenzothiophene-2-carboxylic acid chloride (CA Reg.No. 107943-19-1) in 60ml of toluene at room temperature with cooling and stirring, and themixture is subsequently stirred at 50° C. for 1 hour. For working-up, 60ml of water are added, the precipitated product is filtered off withsuction and washed with water, and the residue is dried in vacuo at 50°C.

7.0 g (97 % of theory) ofN-(3-chlorophenyl)-benzothiophene-2-carboxamide of melting point 179° C.are obtained.

Example II-2 ##STR12##

1.6 g of pulverized potassium hydroxide (88 per cent pure) and 1.0 g ofpalladium on active charcoal (10 per cent) are added to 7.2 g (0.025mol) of 3-chloro-benzothiophene-2-carboxanilide in 25 ml ofN-methylpyrrolidone at room temperature and the mixture is subsequentlyhydrogenated at 50° C. and a hydrogen pressure of 50 bar for 8 hours.For working-up, the catalyst is filtered off and washed twice using ineach case 5 ml of N-methylpyrrolidone, the filtrate is concentrated invacuo, the residue is treated with water, and the precipitated productis filtered off with suction, washed with water and dried.

5.5 g (86 % of theory) of benzothiophene-2-carboxanilide of meltingpoint 188° C. are obtained.

The following benzothiophenecarboxamide S-oxides of the formula (I) areobtained in a corresponding manner and following the general preparationinstructions:

    __________________________________________________________________________     ##STR13##                                                                    Ex. No.                                                                             ##STR14##                                                                                        ##STR15##                                                                              R.sup.7                                                                          Melting point/°C.                 __________________________________________________________________________     2                                                                                  ##STR16##                                                                                        ##STR17##                                                                              H  65-69 (R form)                            3                                                                                  ##STR18##                                                                                        ##STR19##                                                                              H  68-71                                     4   NH-n-C.sub.4 H.sub.9                                                                              ##STR20##                                                                              H  139-141                                   5                                                                                  ##STR21##                                                                                        ##STR22##                                                                              H  194                                       6                                                                                  ##STR23##                                                                                        ##STR24##                                                                              H  oil                                       7   NH-n-C.sub.3 H.sub.7                                                                              ##STR25##                                                                              H  158-160                                   8   NHC.sub.6 H.sub.5                                                                                 ##STR26##                                                                              H  228                                       9                                                                                  ##STR27##                                                                                        ##STR28##                                                                              H  >200                                     10                                                                                  ##STR29##                                                                                        ##STR30##                                                                              H  >200                                     11                                                                                  ##STR31##                                                                                        ##STR32##                                                                              H  >200                                     12   N(CH.sub.3)C.sub.6 H.sub.5                                                                        ##STR33##                                                                              H  98                                       13                                                                                  ##STR34##                                                                                        ##STR35##                                                                              H  >200                                     14                                                                                  ##STR36##                                                                                        ##STR37##                                                                              H  >200                                     15   NH-i-C.sub.4 H.sub.9                                                                              ##STR38##                                                                              H  168-170                                  16   NH-t-C.sub.4 H.sub.9                                                                              ##STR39##                                                                              H  132-134                                  17                                                                                  ##STR40##                                                                                        ##STR41##                                                                              H  >270                                     18                                                                                  ##STR42##                                                                                        ##STR43##                                                                              H  68                                       19                                                                                  ##STR44##                                                                                        ##STR45##                                                                              H  217-219                                  20                                                                                  ##STR46##                                                                                        ##STR47##                                                                              H  194-196                                  21   NH-n-C.sub.12 H.sub.25                                                                            ##STR48##                                                                              H  114-117                                  22   NHC(CH.sub.3).sub.2C.sub.2 H.sub.5                                                                ##STR49##                                                                              H  108-110                                  23                                                                                  ##STR50##                                                                                        ##STR51##                                                                              H  177-179                                  24                                                                                  ##STR52##                                                                                        ##STR53##                                                                              H  203-204                                  25                                                                                  ##STR54##                                                                                        ##STR55##                                                                              H  203-205                                  26   N(n-C.sub.4 H.sub.9)C.sub.6 H.sub.5                                                               ##STR56##                                                                              H  130-132                                  27                                                                                  ##STR57##                                                                                        ##STR58##                                                                              H  76                                       28                                                                                  ##STR59##                                                                                        ##STR60##                                                                              H  240-242                                  29                                                                                  ##STR61##                                                                                        ##STR62##                                                                              H  210-212                                  30                                                                                  ##STR63##                                                                                        ##STR64##                                                                              H  208-210                                  31                                                                                  ##STR65##                                                                                        ##STR66##                                                                              H  205-206                                  32   NHCH.sub.2C.sub.6 H.sub.5                                                                         ##STR67##                                                                              H  209-210                                  33   N(C.sub.2 H.sub.5)C.sub.6 H.sub.5                                                                 ##STR68##                                                                              H  117-120                                  34                                                                                  ##STR69##                                                                                        ##STR70##                                                                              H  192-194                                  35                                                                                  ##STR71##                                                                                        ##STR72##                                                                              H  223-225                                  36                                                                                  ##STR73##                                                                                        ##STR74##                                                                              H  225-228                                  37                                                                                  ##STR75##                                                                                        ##STR76##                                                                              H  65                                       38                                                                                  ##STR77##                                                                                        ##STR78##                                                                              H  211                                      39                                                                                  ##STR79##                                                                                        ##STR80##                                                                              H  217-219                                  40   NH-i-C.sub.4 H.sub.9                                                                              ##STR81##                                                                              Cl 152-154                                  41                                                                                  ##STR82##                                                                                        ##STR83##                                                                              Cl 214-216                                  42                                                                                  ##STR84##                                                                                        ##STR85##                                                                              Cl 225-227                                  43                                                                                  ##STR86##                                                                                        ##STR87##                                                                              Cl 199-200                                  44                                                                                  ##STR88##                                                                                        ##STR89##                                                                              Cl 190-192                                  45   NH(CH.sub.2).sub.2C.sub.6 H.sub.5                                                                 ##STR90##                                                                              Cl 152-153                                  46   N(CH.sub.3)CH.sub.2C.sub.6 H.sub.5                                                                ##STR91##                                                                              Cl 115-118                                  47                                                                                  ##STR92##                                                                                        ##STR93##                                                                              Cl 220-222                                  48                                                                                  ##STR94##                                                                                        ##STR95##                                                                              Cl 223-225                                  49                                                                                  ##STR96##                                                                                        ##STR97##                                                                              Cl 160-162                                  50                                                                                  ##STR98##                                                                                        ##STR99##                                                                              Cl 259-261                                  51                                                                                  ##STR100##                                                                                       ##STR101##                                                                             Cl 220-222                                  52                                                                                  ##STR102##                                                                                       ##STR103##                                                                             Cl 138-139 (diastereomer A)                 53                                                                                  ##STR104##                                                                                       ##STR105##                                                                             Cl 173-175                                  54                                                                                  ##STR106##                                                                                       ##STR107##                                                                             Cl 245                                      55                                                                                  ##STR108##                                                                                       ##STR109##                                                                             Cl 138-139 (diastereomer B)                 56                                                                                  ##STR110##                                                                                       ##STR111##                                                                             Cl 55-58                                    57                                                                                  ##STR112##                                                                                       ##STR113##                                                                             Cl 75 (R form)                              58   NHCH.sub.2C.sub.6 H.sub.5                                                                         ##STR114##                                                                             Cl 152-154                                  59                                                                                  ##STR115##                                                                                       ##STR116##                                                                             Cl 172-174                                  60                                                                                  ##STR117##                                                                                       ##STR118##                                                                             Cl 168                                      61                                                                                  ##STR119##                                                                                       ##STR120##                                                                             Cl 230-232                                  62                                                                                  ##STR121##                                                                                       ##STR122##                                                                             Cl 261-263                                  63                                                                                  ##STR123##                                                                                       ##STR124##                                                                             Cl 194                                      64                                                                                  ##STR125##                                                                                       ##STR126##                                                                             Cl 137-139 (diastereomer A)                 65   N(C.sub.2 H.sub.5)C.sub.6 H.sub.5                                                                 ##STR127##                                                                             Cl 135-137                                  66                                                                                  ##STR128##                                                                                       ##STR129##                                                                             Cl 177-179                                  67                                                                                  ##STR130##                                                                                       ##STR131##                                                                             Cl 192-193                                  68                                                                                  ##STR132##                                                                                       ##STR133##                                                                             Cl 197-199                                  69                                                                                  ##STR134##                                                                                       ##STR135##                                                                             Cl 158 (diastereomer B)                     70                                                                                  ##STR136##                                                                                       ##STR137##                                                                             Cl 192-193                                  71                                                                                  ##STR138##                                                                                       ##STR139##                                                                             Cl 193                                      72                                                                                  ##STR140##                                                                                       ##STR141##                                                                             Cl 188-190                                  73                                                                                  ##STR142##                                                                                       ##STR143##                                                                             Cl 209-210                                  74                                                                                  ##STR144##                                                                                       ##STR145##                                                                             Cl 172-174                                  75                                                                                  ##STR146##                                                                                       ##STR147##                                                                             Cl 172                                      76                                                                                  ##STR148##                                                                                       ##STR149##                                                                             Cl 188-190                                  77                                                                                  ##STR150##                                                                                       ##STR151##                                                                             Cl 198-200                                  78   N(n-C.sub.4 H.sub.9)C.sub.6 H.sub.5                                                               ##STR152##                                                                             Cl 153                                      79                                                                                  ##STR153##                                                                                       ##STR154##                                                                             Cl 60                                       80                                                                                  ##STR155##                                                                                       ##STR156##                                                                             Cl 214-216                                  81                                                                                  ##STR157##                                                                                       ##STR158##                                                                             Cl 194                                      82                                                                                  ##STR159##                                                                                       ##STR160##                                                                             Cl 149-150                                  83                                                                                  ##STR161##                                                                                       ##STR162##                                                                             Cl 169-171                                  84                                                                                  ##STR163##                                                                                       ##STR164##                                                                             H  176-179                                  85                                                                                  ##STR165##                                                                                       ##STR166##                                                                             H  255-256                                  86                                                                                  ##STR167##                                                                                       ##STR168##                                                                             H  218-220                                  87                                                                                  ##STR169##                                                                                       ##STR170##                                                                             H  217-218                                  88                                                                                  ##STR171##                                                                                       ##STR172##                                                                             H  158-159                                  89                                                                                  ##STR173##                                                                                       ##STR174##                                                                             H  225-226                                  90                                                                                  ##STR175##                                                                                       ##STR176##                                                                             H  236-237                                  91                                                                                  ##STR177##                                                                                       ##STR178##                                                                             H  199-201                                  92                                                                                  ##STR179##                                                                                       ##STR180##                                                                             H  208-209                                  93                                                                                  ##STR181##                                                                                       ##STR182##                                                                             H  238-240                                  94                                                                                  ##STR183##                                                                                       ##STR184##                                                                             H  95-97                                    95                                                                                  ##STR185##                                                                                       ##STR186##                                                                             H  121-123                                  96                                                                                  ##STR187##                                                                                       ##STR188##                                                                             H  190-191                                  97   NH(CH.sub.2).sub.6CH.sub.3                                                                        ##STR189##                                                                             H  141                                      __________________________________________________________________________

Use Examples

In the Use Examples which follow, the compound given below was employedas comparison substance: ##STR190##

N-methyl-benzothiophene-2-carboxamide S,S-dioxide (disclosed in DE-OS(German Published Specification) 4 115 184).

Example A

Phytophthora Test (tomato)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 past by weight of alkyl-aryl polyglycol ether

To produce a suitable preparation of active compound, one part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous sporesuspension of Phytophthora infestans.

The plants are then placed in an incubation cabin at 20° C. and arelative atmospheric humidity of about 100%.

The test is evaluated 3 days after inoculation. In this test, a degreeof effectiveness of at least 60 % is shown, for example, by thecompounds of Preparation Examples 8, 9, 10 and 11 at an active compoundconcentration in the spray mixture of 10 ppm, while comparison substance(A) shows no activity.

                                      TABLE A                                     __________________________________________________________________________    Phytophthora test (tomato)/protective                                                                    Degree of effectiveness in % of the                                           untreated control at an active                     Active compound            compound concentration of 10                       __________________________________________________________________________                               ppm                                                 ##STR191##                0                                                   ##STR192##                72                                                  ##STR193##                66                                                  ##STR194##                81                                                  ##STR195##                62                                                 __________________________________________________________________________

Example B

Protection of materials test

To detect an antifungal action, the minimum inhibitory concentrations(MIC values) of compounds according to the invention are determined:

An agar prepared using malt extract is treated with active compoundsaccording to the invention in concentrations from 0.1 mg/l to 5,000mg/l. After the agar has solidified, it is contaminated with purecultures of Penicillium brevicaule, Chaetomium globosum and Aspergillusniger. After the agar plate had been stored for two weeks at 28° C. anda relative atmospheric humidity of 60 to 70%, the minimum inhibitoryconcentration (MIC value) is determined. The MIC value characterizes thelowest concentration of active compound at which no growth whatsoever ofthe microbe species used is observed on the agar.

In this test, a minimum inhibitory concentration of in some cases lessthan 50 mg/l is shown, for example, by the compounds of the followingpreparation examples: 4, 7, 15, 16, 18, 22, 23, 27, 35, 36, 37, 38, 56,58, 63, 65, 66, 67, 68, 70, 72, 73, 74, 75, 80, 82 and 83.

                                      TABLE B                                     __________________________________________________________________________    Protection of materials test                                                                             Minimum inhibitory concentration                                              (MIC value) in mg/l                                Active compound            Penicillium                                                                         Chaetomium                                                                          Aspergillus                            __________________________________________________________________________     ##STR196##                <50   <50   200                                     ##STR197##                <50   75    200                                     ##STR198##                75    75    200                                     ##STR199##                100   100   300                                     ##STR200##                <50   100   200                                     ##STR201##                100   100   200                                     ##STR202##                <50   <50   75                                      ##STR203##                <50   150   200                                     ##STR204##                <50   <50   <50                                     ##STR205##                <50   400   >600                                    ##STR206##                75    100   200                                     ##STR207##                <50   <50   600                                     ##STR208##                <50   <50   <50                                     ##STR209##                <50   <50   <50                                     ##STR210##                <50   <50   75                                      ##STR211##                200   100   200                                     ##STR212##                <50   <50   <50                                     ##STR213##                <50   <50   >600                                    ##STR214##                <50   <50   >600                                    ##STR215##                <50   <50   <50                                     ##STR216##                <50   <50   <50                                     ##STR217##                <50   <50   75                                      ##STR218##                <50   <50   <50                                     ##STR219##                <50   <50   <50                                     ##STR220##                >600  600   >600                                    ##STR221##                <50   <50   <50                                     ##STR222##                <50   <50   <50                                    __________________________________________________________________________

It must be mentioned that the description and the examples illustratethe present invention, but do not impose any limitation, and that otherembodiments in connection with the principle and scope of the inventionwill be self-evident for those skilled in the art.

We claim:
 1. A benzothiophenecarboxamide-S-oxide of the formula##STR223## in which R¹ represents straight-chain or branched alkylhaving 1 to 18 carbon atoms,or represents cycloalkyl having 3 to 6carbon atoms,or represents arylalkyl, or aryl, each of which has carbonatoms in the aryl moiety and up to 8 carbon atoms in the straight-chainor branched alkyl, moiety and each of which is optionally mono- totrisubstituted in the aryl moiety by identical or differentsubstituents, selected from the group consisting of halogen, nitro,straight-chain or branched alkyl, or alkoxy each of which has 1 to 4carbon atoms, cycloalkyl having 3 to 7 carbon atoms, straight-chain orbranched halogenoalkoxy which has 1 to 4 carbon atoms and 1 to 9identical or different halogen atoms, or straight-chain or branchedalkylcarbonyl, R² represents hydrogen or represents straight-chain orbranched alkyl having 1 to 4 carbon atoms, R³, R⁴ R⁵ and R⁶ representhydrogen, and R⁷ represents hydrogen or chlorine.
 2. Abenzothiophenecarboxamide S-oxide according to claim 1, in whichR¹represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- ori-pentyl, n- or i-hexyl, n- or i-heptyl, n- or i-octyl, n- or i-nonyl,n- or i-decyl, n- or i-dodecyl, or n- or i-octadecyl, or representscycloopropyl, cyclopentyl, cyclohexyl, or furthermore, representsphenylalkyl, or phenyl each of which has, up to 6 carbon atoms in thestraight-chain or branched alkyl, moiety and each of which is optionallymono- to trisubstituted by identical or different substituents, whereinthe aryl substituents are selected from the group consisting offluorine, chlorine, bromine, nitro, methyl, ethyl, n- or i-propyl, n-,i-, s-or t-butyl, methoxy, ethoxy, n-or i-propoxy, n-, i-, s-ort-butoxy, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl,trifluoromethoxy, methylcarbonyl and ethylcarbonyl. R² representshydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- ori-hexyl, R³, R⁴, R⁵ and R⁶ represent hydrogen and R⁷ represents hydrogenor chlorine.
 3. A microbicidal composition comprising a microbicidallyeffective amount of a benzothiophenecarboxamide S-oxide according toclaim 1 and an inert diluent.
 4. A method of combatting undesiredmicroorganisms in plant protection and in the preservation of materials,which method comprises applying to such undesired microorganisms or thetheir habitat a microbicidally effective amount of a compound accordingto claim 1.